Phenols from cashew nut shell liquid and method of obtaining the same



. Patented Oct; 22, 1940 UID .AND METHOD OF vSAME OBTAINING THE Mortimer T. Harvey, East Orange, N. J., as-

signor to The Harvel C of New Jersey orporation, a corporation No Drawing. Application April 22, 1937,

v 6 Claims.

The present invention relates generally, to products obtained by cracking and distilling cashew nut shell liquid, to the residues from such distillations, and to methods and steps of making such distillations and of treating intermediate Serial No. 138,3

I have discovered that a valuabl preparation having a high germicidal coefilcient can be made from cashew nut shell liquid by the method and steps hereinafter fully set forth. The exact composition of these preparations has not yet been a products thereof to secure other products of the determined. These compounds however are invention. The products of the invention are 'much stronger in germicidal effect than phenol useful as and in the arts of germicides, colors, and a sample mixture comprising 30% of a proddyes, perfumes, flavors, solvents and plasticizers uct of the invention and 70% of water gave a for cellulose esters, and bases for the several ones phenol coefficient'of 5.25 in a germicidal test on 10 of these products, for making resins for coatings, Bacillus typhosus made with the 1921 modiflcamolded and other products, and for use in the arts tion of Rideal-rWalker method. generally. The details of this particular test are given in Methods and steps for producing all of the the table below. The germicidal product referred l'i above products will be given below, but'at the to in the above paragraph is denoted as disin- 16 first my disclosure will be directed more particufectant" in the table below and is compared with larly to the making of germicides with other prodphenol. H ucts or intermediates therefor. Germicidal test Certain inventions described herein, but not Rideal-Walker method (1921 modification) on claimed, are claimed in my copending application Organism--B. typhosus (Hopkins) Serial Number 303,815, filed November 10, 1939. Age of cu1ture24 hours at 3'7 C. 1 It is well known that raw cashew nut shell Medium-Rideal-Walker beef extract broth liquid has been used for many years, particularly Organic matterNone in India, for purpose of protecting furniture, tim- Temperature of medicati0n18C.

bers, and so on against certain species of ants and D0se=0.5 c. c. of filtered culture to 5 c. c. of diluted 25 other insects which devour wood, but the raw disinfectant cashew nut shell liquid does not have the germi- Subcultures=0ne 4 mm. loopful to 10 c. c. of broth cidal qualities of the products of the invention and The subcultures were incubated 4'7 hours at 37 has the disadvantage of a vesicant action on the C. with the following results:

Minutes of exposure to disinfectant Sample Dilution M00 Disinfectant (30% solids) rec'd 9/29/30. 15550 1:600 Phenol skin, not present in the products of the present 450 550 invention. Phenol coeflicient =525 Raw cashew nut shell liquid is composed of v 45 about ninety per cent of anacardic acid and about For p poses of exampl W methods of in ten per cent of cardol. By the distilling steps of the germicidal preparations of the invention are the present invention these materials are for the given bel w, identified respectively its method most part cracked or dissociated to form com A and method B. In both these methods the paratively large molecule phenols, water and cashew nut shell liquid used was given a prelimi- 50 some other materials. The phenols produced are nary he at b to drive Off moisture non-toxic, can be separated from the other prod- C ined therein whereby frothing Would be ucts of the distillation and have various other avoided in heating at t e h h t p a ur s haracteristics and-the other products have useshown in the disclosure of these methods. Hereful applications, as set forth hereinafter, inafter the cashew nut shell liquid which has been 55 given the preliminary heating is referred to as dehydrated cashew nut shell liquid or the dehydrated liquid.

' Method 1.In one method of the invention a quantity of the dehydrated liquid was cracked and distilled at atmospheric temperature from a copper container through an iron pipe, until a residue was left which was approximately 50% of the weight of the original amount of dehydrated oil used. A thermometer used to determine the temperature had its bulb at the bottom of an iron tube which latter had its closed inner end extending into the liquid and its outer open end sealed at an opening in the cover of the copper container. A quantity of cylinder oil was placed in the tube containing the thermometer to immerse the thermometer bulb for the purpose of protecting the latter against suddenchanges in temperature. The distillation started with a few drops at about 580 F. at 700 the drops of distillate commenced to flow faster; and the flow of distillate reached approximately maximum at about 720 F. Th bulk of distillate came over between 720 and 730 F. The total distillate, except a water solution B which separates out at the bottom, is identified here as distillate A for convenience in setting forth the methods of the invention. P

The residue, 0, is a tarry looking substance which I have found to be very black, is oil soluble; and is valuable for use in japans, paints, enamels and the like because of the above given qualities and particularly because it gives a real black color when used with vehicles such as linseed oil, China-wood oil and cashew nut shell liquid. This oil soluble black residue and materials made therefrom will be claimed in a divisional patent application drawn thereto.

To 100 parts of distillate A were added about parts of powdered caustic soda, by weight, and placed in a glass container under a reflux condenser. and heated for about 2% hours at about 300 F.

The refluxed liquid was distilled at about 300 F. and the distillate D and residue E saved. Distillate D is useful as a solvent for cellulose acetate and cellulose nitrate lacquers, and oil paints and varnishes.

The residue E is then added to an equal volume of water for removing water solubles formed during or remaining after the reaction with caustic under the reflux. This mixture was separated in a separatory funnel into water solution F and liquid G. The solution F is the "disinfectant set forth in the Rideal-Walker test table given above. v

The liquid G is a base for making dyes, perfumes and flavors by various reactions such as. nitration, reduction, and reactions with metals.

This liquid G- contains a breakdown product of anacardic acid called "CardanoP, described and claimed in my copending application Ser. No; 703,414. Cardanol can be separated by distillation, for example, at about 199 to 200 C. at about 7 to 9 millimeters pressure and is suitable for making resins, factis, coatings, molded products and the like as by reaction with formaldehyde, acids such as sulphuric, hydrochloric and so on. driers such as lead oxide, manganese dioxide and other well known commercial driers. It can be used for making resins with the cresols (for example, any of the cresylic acids) and formaldehyde, which resins are soluble in China-wood oil,

linseed oil or other drying oils, or in varnishes made of any of these oils. -A resin made of two parts cresylic acid and one part anacardic acid by weight with about five to ten per cent formaldehyde, ror exam le, is soluble in equal parts and other ratios of China-wood, linseed or other drying oils or varnish thereof. Like anacardic acid Cardanol can also be used in making glyptal 5 type resins with glycerine and phthalic anhydride 7 by substituting it ior oleio or corresponding acid in molecule proportion in various ones of the formulas given in the literature.

Method 2.A second method differs from Method I in that the entire distillate at the beginning, that is, distillate A and water solution B, was placed in a separatory funnel and let stand to allow distillate A and the water solution B to separate more fully. Distillate A is then distilled at a range of about 140 to 290 F. to secure a liquid distillate H and liquid residue 1. To 100 parts of residue I were added about 15 parts by weight of powdered caustic soda and the mix: ture heated for about 2 hours at about 300 F. under a reflux condenser, after which it was allowed to cool and about an equal volume of water was added and let stand in a separatory funnel. Separation took place into two layers consisting of an upper liquid K corresponding to liquid G above and a lower water solution L, which latter is a germicide like solution F of Method 1 above.

Method 3.A third method or variation is to distill distillate A, of Method 1 or 2, in a range of about 300 to 460 F. to secure a residue M and a distillate N. The residue M corresponds to liquid G and liquid K. above, contains Cardanol, and is suitable for the purposes given therefor to which reference is hereby made. Distillate N, when treated with caustic or alcohol, to form a liquid 0, is a germicide and corresponds to solution F and solution L above.

Solution F, solution L and liquid 0 are suitable for use for hygienic purposes and for general disinfection of walls, floors and other places, generally with dilution with water, with or without the addition of soda, soaps, alcohol or the like to aid in making a solution. Also, for hygienic and other purposes, the caustic can be entirely removed or the amount decreased, by neutralizing with an acid such as hydrochloric and removing the neutralized germicide from the water solution of caustic. The neutralized germicide when diluted with alcohol, or with water with the addition of small amounts of caustic, and/or alcohol to aid in solution is again for general use.

In the above Methods 1, 2 and 3 caustic materials other than caustic soda can be used for refluxing, for example, caustic potash, soda ash, sodium bicarbonate, ammonium carbon, ammonium hydroxide, lime, rosin or soya bean soaps and other soaps and so on. Also in place of using solid caustic material, caustic solutions can be used. These materials can also be used in preparing solutions or dispersions of the germicide for use. For this latter purpose gum arabic, agar-agar and furfur-aldehyde can be used. A notable characteristic of the germicide of the invention, for example, solution F, solution L, and liquid 0, is that it is not toxic, in remarkable contrast to phenol and.cresols which are well known to be highly toxic.

From the above descriptions of the germicide of the present invention and of the methods and steps in producing the same, it appears that the germicide of the invention is that part of cashew nut shell liquid distillate which is miscible with water in the presence of caustic.

Cashew nut shell liquid is destructively dis- 75 tilled with steam, for example, at between 230 F. and 300 F. to bring over a phenol which is insoluble in water and insoluble in alkaline solutions and in the residue left after the distillate is a phenolic compound which is insoluble in water and insoluble in alkaline solutions. The residue and the distillate phenols are each reactive with aldehydes (e. g. formaldehyde) to produce resinous condensation products.

When about 50% to about 75% of the cashew nut shell liquid has been removed by destructive distillation either with or without steam and at normal pressure or at reduced pressure the residue is of heavier viscosity than cashew nut shell liquid, and with the greater degree of distillation reaches a thick tarry state.

Having thus described my invention what claim and desire to protect by Letters Patent is:

1. The method which comprises destructively distilling cashew nut shell liquid and separating alkali insoluble phenols from the distillate and the residue.

2. The alkali insoluble phenols produced by the destructive distillation of cashew nut shell liquid.

3. A cracked distillate product of cashew nut shell liquid obtained at a temperature range between 650 and 750 F., approximately, said distillate being liquid at normal temperatures and being insoluble in water and in alkaline solutions.

4. The tarry residual products obtained by distilling cashew nut shell liquid at a temperature between about 650 F. and 750 F.

5. That part of the liquid product obtained by distilling cashew nut shell liquid up to about 750 F. which is insoluble in water and insoluble in caustic soda solution.

. 6. The water and alkali insoluble phenolic residue left when cashew nutshell liquid is destructively distilled with steam.

MORTIMER T. HARVEY. g 

